CN105585441A - Method used for producing 1,3-propanediol - Google Patents

Method used for producing 1,3-propanediol Download PDF

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CN105585441A
CN105585441A CN201410575052.1A CN201410575052A CN105585441A CN 105585441 A CN105585441 A CN 105585441A CN 201410575052 A CN201410575052 A CN 201410575052A CN 105585441 A CN105585441 A CN 105585441A
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catalyst
reaction
carrier
hydroformylation
acetoxyl group
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CN105585441B (en
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查晓钟
杨运信
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method used for producing 1,3-propanediol. The invention mainly aims at solving problems of low activity and low selectivity of 1,3-propanediol catalysts in prior arts. The method mainly comprises the following steps: vinyl acetate is subjected to hydroformylation, such that 3-acetoxypropionaldehyde is obtained; 3-acetoxypropionaldehyde is hydrogenated, such that 3-acetoxypropanol is obtained; and 3-acetoxypropanol is subjected to alcoholysis, such that 1,3-propanediol is obtained. A hydroformylation catalyst comprises a main catalyst and an accelerant. The main catalyst comprises a carrier and an active component. The active component is a rhodium compound. The accelerant is at lease one selected from organic amine and organic phosphorus. The carrier is silicon dioxide which has an aluminum coating on the surface and which is modified with modification metal element. The modification metal element is at least one selected from IIB metal elements. With the technical scheme, the problem is well solved. The method can be applied in 1,3-propanediol industrial production.

Description

For the production of the method for 1,3-PD
Technical field
The present invention relates to the method for the production of 1,3-PD.
Background technology
1,3-PD (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, washing agent, anticorrisive agent,Synthesizing of emulsifying agent, also for industries such as food, cosmetics and pharmacy. Because it is a kind of important polyester fiber monomer,Its topmost purposes is as monomer and terephthalic acid (TPA) synthesizing new polyester material one polytrimethylene terephthalate(PTT)。
The preparation method of 1,3-PD has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehydeStiasny method, acrylate method, bioanalysis, vinyl acetate hydroformylation etc. At present, the industrialization of 1.3-PDO is rawProduct method is chemical synthesis, and international market is mainly by German Degussa company, shell Shell company of the U.S. and the U.S.Three monopolizations of E.I.Du Pont Company. What Degussa company adopted is that acrolein hydration hydrogenation method (AC method), Shell Co. Ltd adoptWhat be that oxirane carbonyl method (EO method), E.I.Du Pont Company adopt is the own thorugh biologic engineering method (MF method) of innovating. WhereinOxirane two-step process and acrolein hydration method technique are current main flow technique.
It is former in the patents such as patent US4072709 (ProductionofLacticAcid), having told about and having utilized vinyl acetateMaterial, is catalyst by adopting homogeneous phase rhodium compound, by hydroformylation reaction, obtains 2 (or 3)-acetoxyl groups thirdAldehyde. Separate or do not separate, then 3-acetoxyl group propionic aldehyde obtains 1.3-PDO by hydrogenation and hydrolytic process. But above-mentioned sideIn preparation 1.3-PDO process, all there is the low and selective not high problem of 1.3-PDO yield in method.
Summary of the invention
Technical problem to be solved by this invention is yield and the selective low problem of 1,3-PD, provides a kind of newFor the production of the method for 1,3-PD, the method has 1,3-PD yield height and selective high feature.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: for the production of the method for 1,3-PD,Comprise the following steps: (1) is taking vinyl acetate, carbon monoxide and hydrogen as raw material, under hydroformylation catalyst existsCarry out hydroformylation reaction and obtain 3-acetoxyl group propionic aldehyde; (2) under hydrogenation catalyst exists, make hydrogen and 3-acetylThe reaction of oxygen base propionic aldehyde obtains 3-acetoxyl group propyl alcohol; (3) hydrolysis of 3-acetoxyl group propyl alcohol obtains 1,3-PD; Wherein,Hydroformylation catalyst comprises major catalyst and promoter, and major catalyst comprises carrier, active component; Adopt for described active groupWith the compound of rhodium; Described promoter is selected from least one in organic amine and organophosphor; Described carrier is for containing on its surfaceAluminized coating and with the element modified silica of modified metal; Described aluminium content is 1.00～10.00g/L; Modified metal unitCellulose content is 0.010～1.00g/L; Described modified metal element is selected from least one in IIB metallic element. Preferably instituteState organophosphor and there is the structure as shown in the formula (I), more preferably R1、R2And R3For alkyl, be further independently selected from C1～C20Alkyl, further independent preferably from C6～C20Aryl or alkyl substituting aromatic base, for example phenyl, tolyl, naphthylDeng.
The compound of rhodium described in technique scheme is preferably RhCl3. Described promoter is preferably pyridine and triphenyl phosphorusAt least one. Described aluminized coating raw material is selected from aluminium hydroxide, boehmite, boehmite and aluminum phosphate at leastA kind of. Preferably at least one in Zn, Cd and Hg of described IIB metallic element. More preferably described IIB metallic elementComprise Zn and Cd simultaneously.
State in technical scheme, the concrete technology condition of the hydroformylation reaction of step (1) is not key of the present invention, andAnd those skilled in the art can rationally determine according to actual needs. The concrete technology of the hydroformylation reaction of step (1)Condition, such as but not limited to: the temperature of hydroformylation reaction is 50～180 DEG C; The pressure of reaction is 1.0～15.0MPa;The time of reaction is 1.0～15.0h; Carbon monoxide and hydrogen volume ratio are 0.10～10.0.
In technique scheme, described hydroformylation catalyst, the optional preparation method who comprises the steps obtains:
1. described aluminized coating raw material and Ludox are mixed to get to coating liquid;
2. above-mentioned coating liquid is coated to silica surface, dry, roasting obtains described catalyst carrier precursor I;
3. be immersed in catalyst carrier precursor I dry obtaining by being mixed with the aqueous solution containing the compound of IIB metallic elementDescribed catalyst carrier II;
4. press the composition of catalyst by RhCl3II mixes with catalyst carrier;
5. standing, dry, roasting, obtains described major catalyst.
In technique scheme step 3. described baking temperature be preferably 80～120 DEG C. More preferably 100～120 DEG C.
The preparation key of catalyst of the present invention is the preparation of hydroformylation major catalyst, after obtaining major catalyst, logicalCross and make major catalyst can obtain catalyst of the present invention with described promoter contact. The side that major catalyst contacts with promoterFormula is not particularly limited, to be also not particularly limited the opportunity that both contact. For example catalyst of the present invention can usedBefore chemical reaction, make both contact and form described catalyst, can also make both applied anti-at catalyst of the present inventionAnswer contact in system that catalyst original position is generated.
The present inventor finds, in technique scheme, activity component impregnation is used to aluminum phosphate, hydrogen-oxygen at the same timeChange aluminium do the catalyst that obtains on aluminized coating raw material and the compound modified carrier with Zn and Cd be no matter selectively orIt is best that 1,3-PD yield has all reached.
Key of the present invention is the selection of hydroformylation catalyst, how really according to actual needs those skilled in the art will know thatThe proportioning of fixed suitable reaction temperature, reaction time, reaction pressure and material. But, hydrogen formyl in technique schemeThe temperature of changing reaction is preferably 50～180 DEG C; The pressure of reaction is preferably 1.0～15.0MPa; The time of reaction is preferably1.0～15.0h. The mol ratio of carbon monoxide and hydrogen is preferably 0.10～10.0.
In the method for the synthetic 1,3-PD of the present invention, after step (1) finishes, can be to the mixing of hydroformylation reactionThing separates acquisition target product 3-acetoxyl group propionic aldehyde and carries out step (2) again, also can step (1) generate 3-After acetoxyl group propionic aldehyde, do not separate and directly carry out step (2). Those skilled in the art know the suitable hydrogenation of selection and urgeAgent and definite suitable hydrogenation reaction temperature, time and material proportion. Conventional hydrogenation catalyst has transition metal unitThe metallic catalyst, metal oxide catalyst, metal sulfide catalyst, complex catalyst of element etc., for example platinum, palladium,Nickel, ruthenium carried catalyst, cupric oxide-copper chromite, aluminium oxide-zinc oxide-chromium oxide catalyst, nickel-molybdenum sulphide withAnd RhCl[P (C6H5)3]. In the present invention preferably Raney's nickel as hydrogenation catalyst, suitable hydrogenation temperature is preferably 30～100 DEG C; Preferably 0.5～8.0MPa of hydrogenation reaction pressure; The hydrogenation reaction time is preferably 10～200min; Aldehyde and hydrogenMol ratio preferably 0.10～2.0; Solvent preferred water, at least one in toluene.
After step (2) finishes, can separate and obtain target product 3-acetoxyl group third mixture of hydrogenation reactionAlcohol carries out step (3) again, also can step (2) generates after 3-acetoxyl group propyl alcohol and does not separate and directly carry out step(3). Those skilled in the art know select suitable alcoholysis catalysts and determine suitable alcoholysis reaction temperature, time andMaterial proportion. But in technique scheme in alcoholysis reaction in the preferred base catalyst of alcoholysis catalysts and acidic catalystAt least one; At least one of the low-carbon (LC) saturated alcohols of the preferred C1～C5 of alcohol in alcoholysis reaction. Alcoholysis reaction catalystMore preferably be dissolved in the sodium methoxide of alcohol; More preferably methyl alcohol of alcohol in alcoholysis reaction. In technique scheme, alcoholysis reaction temperatureBe preferably 30～100 DEG C; Preferably 0～2.0MPa of alcoholysis reaction pressure.
End product of the present invention adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) point after cooling, decompression, separationAnalyse, calculate the conversion ratio of vinyl acetate and the yield of 1,3-PD and selective by following formula:
Compared with prior art, key of the present invention is that hydroformylation catalyst carrier uses containing aluminized coating and uses IIB metalElement carries out after modification, is conducive to improve activity and the stability of hydroformylation major catalyst, thereby has improved 1,3-the third twoThe yield of alcohol and selective.
Experimental result shows, adopts the prepared 1,3-PD yield of catalyst of the present invention to reach 75.59%, selectively reachesTo 89.54%, obtain good technique effect. Especially use aluminum phosphate and aluminium hydroxide to do aluminium in catalyst carrierCoating material and with containing Zn with when collaborative containing the modification of Cd metallic element, has obtained more outstanding technique effect. Logical belowThe present invention is further elaborated to cross embodiment.
Detailed description of the invention
[embodiment 1]
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by aluminium-hydroxide powder and concentration containing 5.20gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed inIn 1.0L catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al containsAmount is 5.15g/L, and Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.59% as calculated, is selectively 89.54%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[comparative example 1]
For the comparative example of [embodiment 1].
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, the spherical SiO that is 5.6mm by 1.0L diameter2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG CDry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis,Rh content is 6.45g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 63.26% as calculated, is selectively 82.04%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[comparative example 2]
For the comparative example of [embodiment 1].
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by aluminium-hydroxide powder and concentration containing 5.20gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier II. Carrier is through icp analysis, and Al content is 5.15g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 64.20% as calculated, is selectively 81.88%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[comparative example 3]
For the comparative example of [embodiment 1].
The preparation of hydroformylation catalyst carrier II: by the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O)Aqueous solution 0.6L is immersed in the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C dry, described in obtaining, urgesAgent carrier II. Carrier is through icp analysis, and Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 64.37% as calculated, is selectively 82.64%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
By finding out compared with embodiment 1, the catalyst carrier that the present invention adopts is used containing aluminized coating and use simultaneouslyIIB metallic element carries out the Performance Ratio of modification rear catalyst without the carrier of any modification, than only using the compound modified of aluminiumCarrier, more excellent than the performance of the catalyst of only making with the carrier of IIB metallized metal modification, the choosing of 1,3-PDIt is high that selecting property and yield are all wanted, and these data from embodiment 1, comparative example 1～3 can be found out, the compound containing aluminium has been describedAnd between IIB metal, there is good synergy.
[comparative example 4]
For the comparative example of [embodiment 1].
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by aluminium-hydroxide powder and concentration containing 5.20gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed inIn 1.0L catalyst carrier precursor I, 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 4h, described in obtaining, urgeAgent carrier II. Carrier is through icp analysis, and Al content is 5.15g/L, and Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 65.14% as calculated, is selectively 82.28%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
By finding out compared with embodiment 1, carrier, only carries out carrier containing after the modification of IIB metallic element at dippingThe performance of dry its catalyst of preparing is better than the catalyst performance to taking roasting to prepare after carrier drying, and this is from implementingThe data of example 1, comparative example 4 can be found out.
[comparative example 5]
For the comparative example of [embodiment 1].
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by aluminium-hydroxide powder and concentration containing 5.20gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. Carrier is through icp analysis, and Al content is 5.15g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O, containing the zinc gluconate of 0.60gZn(C12H22O14Zn·3H2O) be dissolved in pure water, obtain maceration extract 500ml, by catalyst carrier II described in 1.0LBe immersed in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtainDescribed major catalyst. Major catalyst is through icp analysis, and Rh content is 6.45g/L, and Zn content is 0.59g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 64.38% as calculated, is selectively 82.56%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
By finding out compared with embodiment 1, together with the active component containing IIB metal and catalyst, flood,The performance of catalyst does not obtain good effect, and these data from embodiment 1, comparative example 5 can be found out. Explanation containsThe compound of aluminium and containing having good synergy between IIB metal.
[embodiment 2]
The preparation of hydroformylation catalyst carrier II: be 35wt% by boehmite powder and concentration containing 5.20gAlLudox 10.0g is fully mixed to get coating liquid, and it is the spherical of 5.6mm that coating liquid is sprayed to 1.0L diameter uniformlySiO2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains instituteState catalyst carrier precursor I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L soaksStain is in 1.0L catalyst carrier precursor I, and 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis,Al content is 5.15g/L, and Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is 6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.58% as calculated, is selectively 89.47%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 3]
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by boehmite powder and concentration containing 5.20gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed inIn 1.0L catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al containsAmount is 5.15g/L, and Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.46% as calculated, is selectively 89.61%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 4]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 5.20gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0LIn catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is5.15g/L, Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.41% as calculated, is selectively 89.44%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 5]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 5.20gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the Cd (OA containing 0.60gCdC)2·2H2O aqueous solution 0.6L is immersed in before 1.0L catalyst carrierBody I is upper, and 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is 5.15g/L, CdContent is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.55% as calculated, is selectively 89.27%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 6]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 5.20gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the HgSO containing 0.60gHg4Be dissolved in and in 8wt% nitric acid, obtain solution 0.6L and be immersed in 1.0L and urgeAgent precursor carrier I is upper, and 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is5.15g/L, Hg content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.62% as calculated, is selectively 89.23%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 7]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 1.10gAl5.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the zinc gluconate (C containing 0.10gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0LIn catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is1.07g/L, Zn content is 0.09g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.39% as calculated, is selectively 89.57%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 8]
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by aluminum phosphate powder and concentration containing 10.00gAlGlue 35.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. By the zinc gluconate (C containing 1.00gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed inIn 1.0L catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al containsAmount is 9.92g/L, and Zn content is 0.99g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.60% as calculated, is selectively 89.78%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 9]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 5.20gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the zinc gluconate (C containing 0.40gZn12H22O14Zn·3H2O), contain the Cd (OA of 0.20gCdC)2·2H2O aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursor I, and 100 DEG C dry obtains described catalyst carrier II.Carrier is through icp analysis, and Al content is 5.15g/L, and Zn content is 0.40g/L, and Cd content is 0.19g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 77.40% as calculated, is selectively 91.12%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
Find out on year-on-year basis by embodiment 9 and embodiment 4 and embodiment 5, improving the selective and yield of 1,3-PDAspect, Zn and Cd have synergy.
[embodiment 10]
The preparation of hydroformylation catalyst carrier II: be that 35wt% silicon is molten by aluminium-hydroxide powder and concentration containing 5.20gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. By the zinc gluconate (C containing 0.40gZn12H22O14Zn·3H2O), containing 0.20gCd'sCd(OAC)2·2H2O aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursor I, and 100 DEG C dry obtains described catalysisAgent carrier II. Carrier is through icp analysis, and Al content is 5.15g/L, and Zn content is 0.40g/L, and Cd content is 0.19g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 77.22% as calculated, is selectively 91.19%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 11]
The preparation of hydroformylation catalyst carrier II: by containing the aluminum phosphate powder of 3.20gAl, containing the hydroxide of 2.00gAlAluminium powder and concentration are that 35wt% Ludox 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to 1.0L uniformlyDiameter is the spherical SiO of 5.6mm2On carrier, under ventilation condition, place 1h, 100 DEG C dry, then at 450 DEG C of barsRoasting 4h under part, obtains described catalyst carrier precursor I. By the zinc gluconate (C containing 0.40gZn12H22O14Zn·3H2O), contain the Cd (OA of 0.20gCdC)2·2H2O aqueous solution 0.6L is immersed in 1.0L catalyst carrier precursor I,100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is 5.15g/L, and Zn content is0.40g/L, Cd content is 0.19g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 108 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 78.37% as calculated, is selectively 92.59%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
Find out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, improving the selective of 1,3-PD and receivingRate aspect, in aluminium source aluminium hydroxide, aluminum phosphate and IIB metal, Zn, Cd have synergy.
[embodiment 12]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 5.20gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0LIn catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is5.15g/L, Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 0.2MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 1.0MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 50 DEG C, the mol ratio of hydrogen and carbon monoxide is 1:10, after sustained response 1.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 70.34% as calculated, is selectively 88.41%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 13]
The preparation of hydroformylation catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 5.20gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the zinc gluconate (C containing 0.60gZn12H22O14Zn·3H2O) aqueous solution 0.6L is immersed in 1.0LIn catalyst carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Carrier is through icp analysis, and Al content is5.15g/L, Zn content is 0.59g/L.
The preparation of hydroformylation major catalyst: by the RhCl containing 6.50gRh3·3H2O is dissolved in pure water, is floodedLiquid 500ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Major catalyst is through icp analysis, and Rh content is6.45g/L。
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 15.0MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 180 DEG C, the mol ratio of hydrogen and carbon monoxide is 10:1, after sustained response 15.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methoxide (CH3ONa)Add 100ml titanium material reactor, first discharge in still and be pressurized to 0.5MPa after air with argon gas, be warming up to 65 DEG C, stirConstant temperature 4h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 76.11% as calculated, is selectively 88.89%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
Table 1
Table 2

Claims (10)

1. for the production of the method for 1.3-propane diols, comprise the following steps: (1) taking vinyl acetate, carbon monoxide and hydrogen asRaw material carries out hydroformylation reaction and obtains 3-acetoxyl group propionic aldehyde under hydroformylation catalyst exists; (2) at hydrogenationUnder catalyst exists, hydrogen is reacted with 3-acetoxyl group propionic aldehyde and obtain 3-acetoxyl group propyl alcohol; (3) 3-acetoxyl groupPropyl alcohol alcoholysis obtains 1.3-propane diols; Wherein, hydroformylation catalyst comprises major catalyst and promoter, major catalyst bagDraw together carrier, active component; Active component adopts the compound of rhodium; Promoter is selected from least one in organic amine and organophosphorKind; Described carrier is that aluminized coating is contained and with the element modified silica of modified metal in its surface; Described aluminium content is1.00～10.00g/L; Modified metal constituent content is 0.010～1.00g/L; Described modified metal element is selected from IIB metalAt least one in element.
2. method according to claim 1, the compound that it is characterized in that described rhodium is RhCl3。
3. method according to claim 1, is characterized in that described its promoter is selected from pyridine and triphenyl phosphorus extremelyFew a kind of.
4. method according to claim 1, it is characterized in that described aluminized coating raw material be selected from aluminium hydroxide, boehmite,At least one in boehmite and aluminum phosphate.
5. method according to claim 1, is characterized in that described IIB metallic element is selected from Zn, Cd and HgAt least one.
6. method according to claim 1, the temperature that it is characterized in that hydroformylation reaction is 50～180 DEG C, reactionPressure is 1.0～15.0MPa, and the time of reaction is 1.0～15.0h.
7. method according to claim 1, is characterized in that in hydroformylation reaction that carbon monoxide and hydrogen volume ratio are0.10～10.0。
8. method according to claim 1, the preparation method of the hydroformylation major catalyst described in it is characterized in that, bagDraw together following steps:
1. described aluminized coating raw material and Ludox are mixed to get to coating liquid;
2. above-mentioned coating liquid is coated to silica surface, dry, roasting obtains described catalyst carrier precursor I;
3. be immersed in catalyst carrier precursor I the dry institute that obtains by being mixed with the aqueous solution containing the compound of IIB metallic elementState catalyst carrier II;
4. press the composition of catalyst by RhCl3II mixes with catalyst carrier;
5. standing, dry, roasting, obtains described major catalyst.
9. method according to claim 1, is characterized in that step (3) alcoholysis catalysts is selected from base catalyst and acidAt least one in property catalyst.
10. method according to claim 1, is characterized in that the alcohol in step (3) alcoholysis reaction is selected from C1～C5At least one of low-carbon (LC) saturated alcohols.
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CN102372603A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol
CN103521268A (en) * 2012-07-03 2014-01-22 中国科学院大连化学物理研究所 Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof

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CN1158603A (en) * 1994-09-30 1997-09-03 国际壳牌研究有限公司 Process for preparing 1,3-alkanediols and 3-hydroxyaldehydes
WO2011075905A1 (en) * 2009-12-25 2011-06-30 Chen Xiaozhou Methods for preparing ester of 1,3-propylene glycol and 1,3- propylene glycol
CN102372603A (en) * 2010-08-26 2012-03-14 中国石油化工股份有限公司 Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111718246A (en) * 2020-07-18 2020-09-29 万华化学集团股份有限公司 Method for synthesizing gamma-alkoxy alcohol

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